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Distribution and Assessment of Fe and Mn in the Coastal Sediments of

Sendang Biru, East Java, Indonesia
To cite this article: Anugrah Ricky Wijaya et al 2018 J. Phys.: Conf. Ser. 1093 012013

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The 2017 International Conference on Mathematics, Science, and Education IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1093 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1742-6596/1093/1/012013

Distribution and Assessment of Fe and Mn in the Coastal

Sediments of Sendang Biru, East Java, Indonesia

Anugrah Ricky Wijaya1,*, Ida Farida1, Atik Sakbaniah1, Anisa Mai Rahmawati1,
Endang Budiasih1, Hasan Daupor2, Md. Sazzad Hossain3, Tatsuya Kunisue4
1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas
Negeri Malang, Jl. Semarang 5 Malang 65145, Indonesia
2
Chemistry Major, Faculty of Science Technology and Agriculture, Yala Rajabhat
University, Yala 95000, Thailand
3
Department of Aquaculture, Faculty of Fisheries, Bangladesh Agricultural University
(BAU), Mymensingh-2202, Bangladesh
4
Environmental Chemistry and Ecotoxicology, Center for Marine Environmental
Studies (CMES), Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577, Japan

*Corresponding author’s email: anugrah.ricky.fmipa@um.ac.id

Abstract. The high presence of heavy metals in sediment can affect the ecological and biological
systems in East Java Indonesia. To monitor the environmental status of Fe and Mn, we
investigated geochemical fraction and distribution of these metals at 8 sites in the sediment of
Sendang Biru. BCR and Tessier sequential leaching methods were applied to leach Fe and Mn,
respectively, due to high precision and accuracy of these methods. The pattern of geochemical
fractions in sediment samples showed the maximum leached levels of Fe and Mn (>50%) in
residual fractions in Sendang Biru Beach, indicating the natural effects surrounding sites. The
portions of Fe and Mn in non-residual fractions located at Sendang Biru Port were higher
compared with the site in the adjacent sea, indicating these metals were derived possibly from
anthropogenic effects. The assessment from CF and I geo calculations of Fe and Mn in sediment
samples showed that the sediment near the Sendang Biru Port was moderately contaminated by
Fe and Mn.

Keywords: Sediment, fraction, BCR, Tessier, leaching, Sendang Biru Beach

1. Introduction
The port in Sendang Biru Beach is one of the famous and big ports in East Java, Indonesia. The
anthropogenic and natural activities can contribute heavy metal in seawater surrounding Sendang Biru
Port. Sediment and coral can be used as media which reflect heavy metal contents including Fe and Mn
in seawater [1]. To understand the Fe and Mn mobilities in each of fraction in sediment associated with
the healthy environment, we used sequential leaching method to evaluate concentration and assessment
of these elements. The dominant presence of Fe and Mn in Sendang Biru sediment suspected influences
ecological and biological systems in the aquatic environment. To understand metals mobility which can
influence environmental systems in Sendang Biru Beach, we used sequential leaching method for Fe
and Mn contents in sediment. These metals have the main pathways residing in their fractions through
chemical and physical processes [2–4]. The adsorption, complexation, and precipitation of Fe and Mn
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The 2017 International Conference on Mathematics, Science, and Education IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1093 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1742-6596/1093/1/012013

in sediment are the main processes of these elements cooperated with iron and manganese hydroxides,
particulate organic matter and clay minerals due to their strong affinities.
Commonly, sequential leaching of Fe and Mn from different sediment fractions were investigated
using Tessier and BCR (Bureau Community of Reference) methods [5,6]. Some researchers recorded
Fe in the fraction of sediment and applied Tessier method releasing with the range 80-100% recovery
[7,8] and 0.74-4.40 %RSD [9,10]. BCR method of leached Mn releasing with the range 95-104
%recovery and 0.80-1.61 %RSD [5,6,11].
Now, the coastal area of Sendang Biru is prepared to improve towards international fishing and others
marine products [12]. It is very important to monitor heavy metals such as Fe and Mn in seawater by
sediment fraction. Here we applied these methods for determining Fe and Mn concentrations in the
geochemical fractions of sediment of Sendang Biru Beach. The major objective of this study was to
elevate the distribution and assessment of Fe and Mn in sediment surrounding Sendang Biru Beach.

2. Experimental Methods
The samples were collected on 12th of November 2016. The sediment samples were taken surrounding
Sendang Biru Port with the geographical location between latitude -8°25'57.9" S and longitude
112°41'02.5" E (Figure 1). The sediments were taken from the surface of Sendang Biru Port with
sediment grab. After the sediment grab was carefully opened, the sediment was transferred into the
plastic bag. The samples were then leached using BCR method to leach Fe and Tessier method to leach
Mn (Table 1).

Figure 1. Sampling Site

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The 2017 International Conference on Mathematics, Science, and Education IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1093 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1742-6596/1093/1/012013

Table 1. The procedure of sequential leaching of BCR and Tessier methods

Fe-BCR Metal Mobility Mn-Tessier Metal mobility
20 mL of CH3COOH 4mL of MgCl2 1 M
0.11 M solution, room solution, pH = 7, room
Acid Soluble (F1) Exchangeable
temperature, shake in 16 temperature, shake in 1
(F1)
hours hour
20 mL of NH2OH.HCl 4 mL of CH3COONa 1 M,
0.5 M solution, pH 2, pH = 5 with CH3COOH, Associated to
Reducible (F2)
room temperature, room temperature, shake in carbonate (F2)
shake in 16 hours 5 hours
5 mL of H2O2 8.8 M
solution, pH 2, room
temperature, shake in 1
hour, repeat in 85 oC,
shake in 1 hour
10 mL of NH2OH.HCl
5 mL of H2O2 8.8 M 0.04 M solution in 25%
Oxidizable (F3) Reducible (F3)
solution, pH 2, 85 oC, CH3COOH solution, 96 oC,
shake in 1 hour shake in 6 hours

25 mL of CH3COONH4
1M, pH 2, room
temperature, shake in 16
hours
1.5 mL of HNO3 0.02 M
solution and 2.5 mL of 30%
H2O2 solution, pH = 2, 85
o
C, shake in 2 hours, add
1.5 mL of 30% H2O2
solution, 85 oC, shake in 3
1 mL of 65% HNO3 hours
solution and 3 mL of 2.5 mL of CH3COONH4 Oxidizable (F4)
36% HCl solution, room 3.2 M solution in 20%
Residual (F4)
temperature, shake in 2 HNO3 solution, room
hours, add temperature, and shake in a
3 drops of HF solution half hour
1 mL of 65% HNO3
solution and 3 mL of 36%
HCl solution, room
temperature, shake in 2 Residual (F5)
hours and add
3 drops of HF solution

3. Results and Discussion

Distribution of Fe and Mn contents in sediment

Fe and Mn concentrations, for the Sendang Biru samples, are reported in Table 2. The content of Fe was
divided into four fractions (F1, F2, F3, and F4) followed by BCR method. The explanation of F1, F2,
F3, and F4 is listed in Table 1. The range of Fe contents in F1, F2, F3, and F4 were 369-5621; 461-
5853; 994-10019; and 5480-25965 mg/Kg and total fraction of Fe contents varied from 7304 to 42884
mg/Kg. The distribution of Fe contents in sediment has the same pattern values from F1 to F3. The

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The 2017 International Conference on Mathematics, Science, and Education IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1093 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1742-6596/1093/1/012013

lowest concentrations of Fe were detected at site 5 and the highest values at site 1. This result indicated
Fe content was contributed by anthropogenic activities in Sendang Biru Port and then continued by the
process of Fe dilution in the open sea.

The chemical reactions in the F1, F2, and F3 can be explained as follows [2]:
F1: Sediment–Fe3+(s) + CH3COOH(aq) ⇄ Sediment–(H)3(s) + (CH3COO)3Fe(aq)
Sediment–Fe2(CO3)3(s) + CH3COOH(aq) ⇄ Sediment(s) + (CH3COO)3Fe(aq) +
H2CO3(aq)
Sediment–Fe2+(s) + CH3COOH(aq) ⇄ Sediment–(H)2(s) + (CH3COO)2Fe(aq)
Sediment–Fe2(CO3)2(s) + CH3COOH(aq) ⇄ Sediment(s) + (CH3COO)2Fe(aq) +
H2CO3(aq)
F2: Sediment–MnO2–Fe(s) + NH2OH.HCl(aq) → Sediment(s) + MnCl2(aq) + FeCl3(aq) +
NH3(g) + H2O(l) + O2(g)
Sediment–MnO2–Fe(s) + NH2OH.HCl(aq) → Sediment(s) + MnCl2(aq) + FeCl2(aq) +
NH3(g) + H2O(l)+ O2(g)
F3: Sediment–HA–Fe(s) + H2O2(aq) + CH3COONH4(aq)→ Sediment–HA(s) +(CH3COO)3Fe(aq)
+ NH3(g) + H2O(l)+ O2(g)
Sediment–HA–Fe(s) + H2O2(aq) + CH3COONH4(aq)→ Sediment–HA(s) +(CH3COO)2Fe(aq)
+ NH3(g) + H2O(l)+ O2(g)

The concentration of Fe in F4 ranged from 5480-25965 mg/Kg (Table 2). The highest portion of Fe
in F4 compared those in F1-F3 suggested the effect of lithogenic and terrestrial associated with natural
source. Fe in F4 refers to the content of Fe in residual fraction. Possible of chemical reaction is followed
[2]:
F4: Sediment–SiO2–Al2O3–Fe(s) + HNO3(aq) + HF(aq) →Fe(NO3)3(aq) + Al(NO3)3(aq) +
SiF4(g) + H2O(l) + H2(g)
Sediment–SiO2–Al2O3–Fe(s) + HNO3(aq) + HF(aq) →Fe(NO3)2(aq) + Al(NO3)3(aq) +
SiF4(g) + H2O(l) + H2(g)

The contents of Mn in each fraction from site 1 to site 8 are listed in Table 2. The leached and
determined of Mn concentrations followed the method by Tessier which divided as five fractions (F1,
F2, F3, F4, and F5) (Table 1). The possibilities of chemical reaction are explained as followed [2]:

F1: Sediment-Mn2+(s) + MgCl2(aq) ⇄ Sediment-Mg2+(s) + 2MnCl2(aq)

F2: Sediment-2MnCO3(s) + 4CH3COONa(aq) ⇄ 2Na2CO3(aq) + 2Mn(CH3COO)2(aq)
F3: Sediment-Fe2O3-Mn(s) + 2NH2OH.HCl(aq) → 2Fe2+(aq) + Cl2(g) + Mn2+(aq) + 2H2O(l)
+ 2NH3(g)
Sediment-Fe(OH)3-Mn(s) + 2NH2OH.HCl(aq) → 2 Fe2+(aq) + Cl2(g) + Mn2+(aq) + H2O(l)
+ 2 NH3(g)
F4: Sediment–HA–Mn(s) + H2O2(aq) + CH3COONH4(aq)→ Sediment–HA(s) + NH3(g) +H2O(l)
+ O2(g) + (CH3COO)2Mn(aq) +
F5: Sediment–SiO2–Al2O3–Fe(s) + HNO3(aq) + HF(aq) → Fe(NO3)2(aq) + Al(NO3)3(aq) +
SiF4(g) + H2O(l) + H2(g)

The patterns of Mn contents in F1 and F2 were the same at site 1 and site 4 and the patterns in F3-
F5 were different at site 2, 4, 5, 6, and 7 (Table 2; Figure 2). The portion of Mn contents in F1 and F2
tended to be stable due to the balance of cation and anion (carbonate) exchange from the open sea. The
proportion of Mn contents ranged from 7.96-16.0 mg/Kg in F1 and 7.26-22.0 mg/Kg in F2 (Table 2).

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The 2017 International Conference on Mathematics, Science, and Education IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1093 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1742-6596/1093/1/012013

Table 2. Distribution of Fe and Mn contents in sediment’s fraction of Sendang Biru Beach

Sampling Fe content (mg/Kg) Mn content (mg/Kg)
Site F1 F2 F3 F4 Total F1 F2 F3 F4 F5 Total
1 5621 5853 10019 17803 39297 16.0 22.0 25.2 8.80 52.4 124
2 5110 5406 9102 15581 35200 8.53 7.94 13.7 5.97 52.0 88.1
3 3806 4049 7108 12921 27884 12.5 13.5 31.0 18.6 53.0 129
4 4541 4592 8156 25595 42884 13.4 21.9 23.4 8.24 44.4 111
5 369 461 994 5480 7304 10.9 10.6 38.5 15.1 201 276
6 1149 1657 2613 7711 13129 11.1 12.6 20.1 7.96 57.6 109
7 2337 2382 4179 11338 20236 9.15 15.2 10.1 5.70 41.6 81.8
8 2969 3207 5628 25965 37769 7.96 7.26 14.0 9.79 77.6 117

The range of total Fe concentrations (7304-42884 mg/Kg) in the coastal area of Sendang Biru
exceeded the chronic criterion for protection of aquatic organism for Fe (~1000 mg/kg) in natural marine
sediment, USA [13]. Conversely, most sediment samples had a range of Mn concentrations (818-276
mg/Kg) that were below the 452 mg/Kg for standard marine sediment ocean [14].

Figure 2. The portion of Fe and Mn Contents in Sediment’s Fraction of Sendang Biru Beach
As shown in Figure 2, the pattern of geochemical fractions in sediment samples showed the maxima
leached levels of Fe and Mn in the residual fraction from site 1 to site 8. The Fe and Mn contents in
sediment possibly were contaminated by natural sources such as soil, agricultural, minerals surrounding
Sendang Biru Beach bounded in silica and alumina. The portions of Fe and Mn in non-residual fractions
were higher in Sendang Biru Port compared with the site in the adjacent sea indicating these metals
possibly from anthropogenic effects.

Assessment of Fe and Mn in Sediment

To understand the level of contamination of Fe and Mn contents in sediment associated with water
pollution, we performed an assessment using the calculation index of status pollution in sediments such
as contamination factor (CF) and geoaccumulation index (Igeo) [3,15]. CF was calculated using
Cmetal/Cbackground. In this study, the content of Fe and Mn at site 7 (the lowest concentration) was
considered as background.

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The 2017 International Conference on Mathematics, Science, and Education IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1093 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1742-6596/1093/1/012013

The classification of CF is explained as follows: CF<1: low contamination factor, 1 ≤ CF < 3:

moderate contamination factor; 3 ≤ CF < 6: considerable contamination factor; CF ≥ 6: very high
contamination factor. As listed in Table 3, the value of CF from site 5 to site 7 in the calculation of Fe
were recorded from 0.36 to 1.00. This indicates that Fe contents at site 5-7 reflected low risk, whereas
the values of Fe contents in sediment from site 1 to site 1 were moderate risk. In the case of CF in Mn
sediment, site 1 to site 8 was categorized as moderate contamination.
The second assessment of Fe and Mn contents using the geo-accumulation index (Igeo). Igeo can be
calculated using Igeo= log2 (Cn/1.5 Bn), whereas Cn is the concentration of Fe or Mn. The value of 1.5 is
the factor of lithogenic effect and Bn is the background as explained C background in CF index. Igeo
value is classified as follows: Igeo ≤ 0, class 0, unpolluted; 0 <Igeo ≤ 1, class 1, from unpolluted to
moderately polluted; and 1<Igeo ≤ 2, class 2, moderately polluted. As listed in Table 3, the Igeo of Fe and
Mn contents ranged from -2.06 to 1.17 indicating the status of quality in sediment categorized from class
0 to class 2. These values reflect the status of sediment in the range from unpolluted to moderately
pollution.
Table 3. Assessment of Fe and Mn in Sediment
Sampling CF Igeo
site Fe Mn Fe Mn
1 1.94 1.52 0.18 0.02
2 1.74 1.08 0.16 -0.32
3 1.38 1.57 -0.13 0.07
4 2.12 1.36 0.28 -0.10
5 0.36 3.37 -2.06 1.17
6 0.65 1.13 -1.21 -0.17
7 1.00 1.00 -1.69 -0.18
8 1.87 1.42 0.51 -0.06

4. Conclusion
In this Sendang Biru area, the majority of geochemical fractions of Fe and Mn contents in sediment were
found within the high portions of Fe and Mn in residual fractions. This can be attributed substantially to
the natural sources such as weathering or leaching of the rocks containing Fe and Mn minerals in the
sediment. The distribution of Fe and Mn contents in non-fraction of sediment surrounding Sendang Biru
Port showed highly compared with those in adjacent of the sea possibly associated with the dilution
process of that metals through the sea current. The assessment of Fe and Mn contents in Sendang Biru
sediment using CF and Igeo revealed moderately health risk.

Acknowledgments
The present work is funded by KEMENRISTEKDIKTI, Fundamental Grant Scheme, 2015-2016, DIPA
Number 042.06-0/2016.

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The 2017 International Conference on Mathematics, Science, and Education IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1093 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1742-6596/1093/1/012013

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